Optical properties and toxicity of undoped and Mn-doped ZnS semiconductor nanoparticles synthesized through the aqueous route

Abstract Undoped and Mn-doped ZnS nanoparticles were synthesized at 95 °C in basic aqueous solution using the nucleation-doping strategy. Various samples of the Mn:ZnS NPs with 5, 10 and 20% of Mn dopant have been prepared and characterized using X-ray diffraction, energy-dispersive X-ray analysis, high resolution electron microscopy and photoluminescence (PL) measurements. When increasing the concentration of manganese Mn, the photoluminescence intensity gradually decreases. The PL spectra of the Mn-doped ZnS nanoparticles at room temperature exhibit both, the 450 nm blue defect-related emission and the 592 nm orange Mn 2+ emission. It is vital to obtain NPs that meet the application requirements, however their environmental toxicity needs to be investigated. In this study, the induction of oxidative stress within the digestive gland of the Ruditapes decussatus organism (clam) is described. Antioxidant enzyme activities (superoxide dismutase (SOD) and catalase (CAT)) as well as malondialdehyde (MDA) levels have been determined in the digestive gland after exposure to 100 μg/L of ZnS, ZnS:Mn (5%), ZnS:Mn (10%) and ZnS:Mn (20%). The nanomaterials studied exhibit different responses in the digestive gland. Undoped Mn-ZnS has no effect on the markers considered, showing the limited interaction between this nanoparticle and the cells of the test organisms. In contrast, Mn-doped ZnS increases the activities of SOD and CAT and the level of MDA species, although this toxicity is highly dependent on the chemical properties of the material. These findings provide ideas for future considerations of ZnS nanoparticles, as well as information on the interaction between these materials and an aquatic environment. These data are the first evidence available of the formation of ZnS NPs using aqueous method and are an indication of the importance of knowing the biological target of the NPs when testing their potential impact on environmental model organisms.